Development and Evaluation of a High Sensitive Atomic Fluorescence Spectrometric System

1引言原子荧光光谱法(AfS)是一种选择性好、检测能力优异的痕量/超痕量元素分析方法,其仪器结构简单、易于维护,在各行业均具有非常广泛的应用基础。因而,研发新型AfS系统,改善仪器检测性能,无疑具有重大的实用意义。增加激发光源强度是提高AfS仪器灵敏度的有效途径之一。文献[1~4]将ICP-AfS/IfS仪器的空心阴极灯(HCl)光源供电方式改变为安培级大电流微秒脉冲供电(HCMP),并成功改善了仪器对Cu,Ag,zn,Al,CA,Eu,yb等元素的检出限。A high sensitive hydride generation( HG) atomic fluorescence spectrometric system was developed using high current microsecond pulsed hollow cathode lamp( HCMP-HCL) as the excitation source and its performance was evaluated.Test results confirmed that the excitation source could give out intensive atomic spectral lines.System precision( RSD,n = 7) was 1.1% for arsenic and 1.4% for selenium.Detection limits( DLs,3) were 0.0066 μg / L and 0.0075 μg / L,respectively.The developed AFS system was proved to have high reliability,low detection limit and remarkable improvement of analysis capability compared with that of commercial AFS instruments.国家重大科学仪器设备开发专项项目(No.2011YQ140149)资

Study on Arsenic/Selenium Speciation Analysis by a Modified High Sensitive Atomic Fluorescence Spectrometric System

将实验室自制的高灵敏度原子荧光光谱系统与色谱分离、在线紫外光前处理装置联用,实现了元素形态的液相色谱分离、在线紫外消解、蒸气发生及原子荧光光谱测定,并以砷、硒两元素为例对系统的分析性能进行研究。样品通过加热混旋提取、离心、过滤,使用反相色谱柱并以5.0 MMOl/l磷酸氢二铵缓冲溶液(PH 5.7)-0.5 MMOl/l四丁基溴化铵(TbAb)-1%甲醇为流动相进行分离;三价砷(ASO3-3)、二甲基砷(dMA)、一甲基砷(MMA)、五价砷(ASO3-4)可在7 MIn内进行分离和测定,硒代胱氨酸(SECyS)、硒代蛋氨酸(SEMET)、四价硒(SEO2-3)、六价硒(SEO2-4)的测定约需11 MIn。在优化实验条件下,方法检出限(dlS,S/n=3)为0.08~0.74μg/l;相对标准偏差(rSd,n=7)为1.4%~7.9%,实际样品的加标回收率为82.5%~116.5%;砷、硒各形态在0.28~40.0μg/l和0.38~80.0μg/l范围内线性良好。建立的联用系统稳定性好、检出限低,可实现样品中低浓度砷、硒形态的准确测定。A self-mode labs high sensitive atomic fluorescence spectrometric detection system combined with liquid chromatography,online ultraviolet photochemical digesting and vapor generation device was established and evaluated.Arsenic and selenium species in various samples were extracted by heating-shaking and centrifugal filtration.All the analytes were separated on a reversed-phase column using mobile phase of 5.0 mmol/L phosphate buffer(pH 5.7)-0.5 mmol/L tetrabutyl ammonium bromide(TBAB)-1% methanol.The separations of AsO3-3,DMA,MMA,AsO3-4and SeCys,SeMet,SeO2-3,SeO2-4were achieved within 7 min and 11 min,respectively.Under the optimized operating conditions,the detection limits(DLs,S/N = 3) were in the range of 0.08-0.74 μg/L,and the relative standard deviations(RSD,n = 7) were 1.4%-7.9%.The standard spiked recoveries for real samples were in the range of 82.5%-116.5%.Linearities were obtained in the ranges of 0.28-40.0 μg/L for arsenic species and 0.38-80.0 μg/L for selenium species.The developed system was successfully applied in the detection of low levels of arsenic and selenium species in matrices.国家重大科学仪器设备开发专项项目(2011YQ140149

Determination of four Sudan dyes in chili oil by high performance liquid chromatography with on-line photochemical derivatization and fluorescence detection

建立了在线光化学衍生、荧光检测、高效液相色谱(HPlC)测定辣椒油中苏丹红Ⅰ、Ⅱ、Ⅲ和b的方法。以乙腈-水为流动相,采用梯度洗脱方式在Sb-C18色谱柱上分离。用实验室自制的程序控制时间/光强光化学反应器作为在线衍生装置,优化了光衍生反应的条件和荧光检测条件。3种不同加标浓度下,辣椒油样品中4种苏丹红染料的加标回收率为81.3%~100.4%。加标水平为0.8 Mg/kg下荧光信号强度的相对标准偏差(rSd,n=6)为2.6%~3.8%。苏丹红Ⅰ、Ⅱ、Ⅲ和b的检出限(lOd)和定量限(lOQ)范围分别为0.009~0.054 Mg/kg和0.030~0.181 Mg/kg,优于传统的HPlC分离、二极管阵列检测器检测方法。该方法具有简单、灵敏、选择性好的特点,适用于食品样品中苏丹红的常规分析。A method for the measurement of Sudan Ⅰ,Sudan Ⅱ,Sudan Ⅲ and Sudan B in chili oil using high performance liquid chromatography(HPLC) with on-line photochemical derivatization and fluorescence detection has been developed.The Sudan dyes were separated on an SB-C18 column in a single run by the mixed mobile phase of acetonitrile-water with a gradient program.A laboratory-built time/energy programmed photochemical reactor(PCR) with an ultraviolet mercury lamp was installed between a photodiode array detector(PDA) and a fluorescence detector(FLD),and it was applied to convert the non-or weakly fluorescent Sudan dyes into fluorescence emission components.The photochemical derivatization conditions and fluorescence detection parameters have been investigated and optimized.The recoveries of the standards spiked in real chili oil samples for all the dyes were 81.3%-100.4%.The relative standard deviations(RSDs,n=6) of the fluorescence signal intensity at the spiked level of 0.8 mg/kg were 2.6%-3.8%.The limits of detection(LODs) were in the range of 0.009-0.054 mg/kg and the limits of quantification(LOQs) were 0.030-0.181 mg/kg,which were better than those of the commonly used HPLC coupled with PDA.The developed method which is simple,sensitive,and selective can be applied to the routine analysis of Sudan dyes.美国Agilent公司高等学校研究基金项

Phthalate Esters in the Environment

通过检索国内外相关文献资料,重点阐述和归纳了邻苯二甲酸酯在生态毒性、来源、环境化学行为及污染现状方面的研究进展。结果表明,邻苯二甲酸酯是一类具有环境内分泌干扰作用的有机污染物,主要来源于人工合成,可通过各种途径进入环境,广泛存在于大气、水体、土壤、沉积物、灰尘等环境介质中,日用消费品中也普遍含有。邻苯二甲酸酯的大量使用所带来的环境污染和人体健康问题应当引起足够重视。In this paper, the research progresses on phthalate esters(PAEs) in toxicity, the sources, environmental chemical behavior, and contamination level are summarized by retrieved literatures home and abroad.It is shown that PAEs are a class of environmental endocrine disrupting compounds which mainly come from artifitial synthetic.PAEs can come into the environment through various pathways and transfer in different environmental matrices, so they exist in the atmosphere, water, soil, sediment, and dust.Furthermore, consumer products generally contain PAEs.Therefore, the problem of environmental pollution and human health caused by the extensive use of PAEs should be paid attention to

Progress on Sample Preparation Techniques for Analysis of Pesticide Residues in Foodstuffs

本文综述了近年来食品中农药残留分析的样品前处理技术 ,重点对超临界流体萃取法在食品农药残留分析中的应用及其联用技术进行了评述 ;同时对固相微萃取、微波辅助萃取和凝胶渗透色谱法进行了总结。对食品中农药残留分析技术的发展方向进行了讨论The progress on sample preparation techniques for analysis of the pesticide residues in foodstuffs was reviewed. The applications of the supercritical fluid extraction (SFE), solid-phase microextraction (SPME) , microwave aided extraction (MAE) and gel permeation chromatography (GPC) in analysis of pesticide residues in foodstuffs were described. Special attention was given to SFE technique and its hyphenation with gas chromatography (GC), high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). The trends of sample preparation techniques for analysis of pesticide residues in foodstuffs were also discussed.福建省自然科学基金重点项目 (B0 2 2 0 0 0 1

Determination of carcinogenic aromatic amines derived from azo colorants in textiles and leather by ultra high performance liquid chromatography-tandem mass spectrometry

建立了超高效液相色谱-串联质谱法(uHPlC-MS/MS)快速测定纺织品和皮革中偶氮染料释放的致癌芳香胺物质的方法。样品前处理采用bS En 14362-1:2012(纺织品)和ISO 17234-1:2010(皮革)方法,然后采用甲醇定容,再用EClIPSE Xdb-C18 rrHd色谱柱进行梯度洗脱分离,流动相为甲醇和水;采用电喷雾正离子模式,并用多反应监测模式(MrM)测定,外标法定量。方法优化了色谱分离条件、质谱碎裂电压、碰撞能量等,并考察了不同样品基质对回收率的影响。方法的定量限小于0.2 Mg/kg;不同基质不同浓度的加标回收率在70%~120%之间(添加水平为500、1 000、1 500μg/l,n=7);相对标准偏差小于15%。该方法的灵敏度远小于欧盟与我国国家标准要求的30 Mg/kg,完全满足其定性定量的检测要求,并且检测速度快,选择性好。A rapid determination method was developed for the quantification and confirmation of 22 carcinogenic aromatic amines derived from azo colorants in textiles and leather by ultra high performance liquid chromatography-tandem electrospray ionization mass spectrometry(UHPLC-MS/MS).The methods of EN 14362-1:2012(for textiles) and ISO 17234-1:2010(for leather) were adopted for sample pretreatment,finally diluted with methanol.The target compounds were separated by an Eclipse XDB-C18 RRHD column and eluted with methanol and water in gradient,and then determined by positive electrospray ionization mass spectrometry under multiple reaction monitoring(MRM) mode.The external standard method was used for the quantitative analysis.The separation conditions,fragment voltages,collision energies,etc.were optimized.The limits of quantification(LOQ) were below 0.2 mg/kg for different compounds,matrix spike recoveries ranged from 70% to 120% at the spiked levels of 500,1 000 and 1 500 μg/L,and the relative standard deviations(RSDs) were less than 15%.The proposed method is rapid,sensitive,accurate and selective.福建省自然科学基金重点项目(B0220001); 远东技术服务有限公司委托项

Simultaneous Determination of Ultra-trace Level of As,Sb,Bi,Ge,Sn and Hg in Coastal and Estuarine Seawater by Chemical Vapor Generation and Inductively Coupled Plasma Mass Spectrometry

建立了化学蒸汽发生(CVg)电感耦合等离子体质谱(ICP MS)同时测定近岸及河口海水中超痕量AS、Sb、bI、gE、Sn和Hg元素的方法。研究了CVg过程中kbH4、盐酸和硫脲的浓度以及样品流速、载气流速、海水样品盐度等对方法分析性能的影响。结果表明,在0.70%盐酸、0.10 g/l硫脲、11.0 g/l硼氢化钾、载气0.40 l/MIn条件下,6种待测元素的信噪比最高。优化实验条件下,AS、Sb、bI、gE、Sn和Hg的质量浓度在0.1~5.0μg/l内呈良好线性,相关系数不低于0.996 6;方法对0.1μg/l加标样品的相对标准偏差(rSd,n=5)为3.9%~8.9%,实际海水样品的加标回收率为89%~112%;方法的流程空白为0.012~0.036μg/l,定量下限(lOQS,10σ)在0.006 7~0.026μg/l之间,可满足近岸及河口海水样品中超痕量元素测定的需要。A chemical vapor generation(CVG) and inductively coupled plasma mass spectrometric(ICP MS) method was proposed for the simultaneous determination of ultra-trace level of As,Sb,Bi,Ge,Sn,and Hg in coastal and estuarine seawater.Effects of operating parameters,including concentrations of KBH4,HCl and thiourea,pump flow rate and carrier gas flow rate on analytical performance were studied.The results showed that good signal to noise(S/N) ratios for all the analysed elements were obtained when 0.70% HCl,0.10 g/L thiourea,11.0 g/L KBH4,and 0.40 L/min carrier gas were used in the CVG procedure.The relative standard deviations(RSDs,n=5) for 0.10 μg/L spiked sample were in the range of 3.9%-8.9%.The spiked recoveries for the seawater samples were between 89% and 112%.The method blanks were in the range of 0.012-0.036 μg/L.The limits of quantitation(LOQs,10σ) for the developed method were obtained between 0.006 7 μg/L and 0.026 μg/L.The method could be applied in the simultaneous determination of As,Sb,Bi,Ge,Sn and Hg in coastal and estuarine seawater.近海海洋环境科学国家重点实验室自主创新项目(MELRI0703

Rapid Determination of Alkylphenol and Alkylphenol Ethoxylates in Leather and Textile by Ultrasonic-assisted Extraction and LC-MS

建立了液相色谱-质谱法测定皮革及纺织品中辛基酚(OP)、壬基酚(nP)、辛基酚聚氧乙烯醚(OPEO)及壬基酚聚氧乙烯醚(nPEO)的分析方法。样品经超声波振荡萃取,C18反相色谱柱进行分离,甲醇-水为流动相,离子源为ESI。OP和nP采用负离子模式,定量离子分别为M/z205、219;OPEO和nPEO采用正离子模式,定量离子分别为M/z229+44nEO和M/z243+44nEO(nEO=3--16)。在优化实验条件下,方法的定量下限为0.25--2.5 Mg/kg,样品加标回收率为92%--107%,相对标准偏差为5.3%--9.5%(50 Mg/kg,n=6)。方法简单、快速、灵敏度高,可满足欧盟等地区对皮革及纺织品中OP、nP、OPEO、nPEO的测定要求。A rapid and simple method was developed for measurement of octylphenol(OP),nonly phenol(NP),polyoxyethylene octylphenol ether(OPEO) and polyoxyethylene nonylphenol ether(NPEO) residues in leather,leather products and textile products,by ultrasonic-assisted extraction and liquid chromatography-mass spectrometry.The analytes were sequentially extracted with 20,20 and 10 mL methanol,and then separated on a C18 column by gradient elution with methanol-water as mobile phase.OP and NP were quantitatively detected with negative-ion electro-spray ionization at m/z 205 and m/z 219,and OPEO and NPEO were measured with positive-ion electro-spray ionization at m/z 229+44nEO and m/z 243+44nEO(nEO=3--16).The result indicated that under the optimized conditions,the spiked recoveries were in the range of 92%-107%,and the relative standard deviations(RSDs) for concentration of 50 mg/kg were between 5.3% and 9.5%(n=6).The quantitation limits were 0.25-2.5 mg/kg.The method was simple,rapid and sensitive,and could meet the relevant requirement of European Union.福建省自然科学基金重点资助项目(B0220001);远东技术服务有限公司委托项

聚二甲基硅烷质量的评估方法

聚碳硅烷(PCS)是生产碳化硅陶瓷和碳化硅纤维的先驱体,由聚二甲基硅烷(PDMS)经高温热解重组获得。文中采用在线热裂解-气相色谱-质谱对PDMS热裂解碎片进行分离和结构分析。通过将不同的PDMS谱图与标准样品谱图进行对比,定量确定不同PDMS的相似度,然后根据PCS的纺丝性能评价PDMS的质量,从而建立PDMS热裂解-气相色谱-质谱图与PDMS质量等级之间的相关性,以及建立以Pearson相关系数为定量指标、评估PDMS质量等级的方法

Preliminary Study of 25 Aromatic Amines in Soil and Sediment Matrices with Solid-Liquid-Liquid Extraction Combining with GC-MS

建立了土壤及沉积物中25种芳香胺的固-液-液萃取及气相色谱-质谱(gC-MS)测定方法。样品中的25种芳香胺在碱性条件下用水-甲基叔丁基醚共同萃取,并考察了碱液浓度对萃取效率的影响。结果表明,优化条件下方法的精密度(rSd)小于18%(n=6),25种芳香胺的回收率有16种在50%以上,方法检出限(lOd,3σ)为0.11--1.90μg/kg。A simple and rapid procedure has been developed for 25 aromatic amines extraction with solid-liquid-liquid phase extraction and measurement by gas chromatography-mass spectrometry(GC-MS).The sample was extracted by methyl tertiary butyl ether(MTBE) under alkaline conditions.The experimental conditions were optimized.The result indicated that,under the optimal conditions,relative standard deviations of the method were less than 18%(n=6).The spiked recoveries of 16 aromatic amines were above 50%.Limits of detection(LOD,3σ) were in the range of 0.11-1.90 μg/kg.福建省自然科学基金重点资助项目(B0220001